Adhesive alpha-olefin inter-polymers

ABSTRACT

The invention relates to novel adhesive alpha-olefin inter-polymers which are largely amorphous and have a Theological behavior that makes them suitable for adhesive use, both without and with minimzed amounts of tackifying resins. Specifically, the invention poly-alpha olefin inter-polymer may be composed of A) from 60 to 94 % of units derived from one alpha mono-olefin having from 3 to 6 carbon atoms and B) from 6 to 40 mol % of units derived from one or more other mono-olefins having from 4 to 10 carbon atoms and at least one carbon atom more than A); and C) optionally from 0 to 10 mol % of units derived from another copolymerizable unsaturated hydrocarbon, different from A) and B); the diad distribution of component A in the polymer as determined by  13 C NMR as described herein showing a ratio of experimentally determined diad distribution over the calculated Bernoullian diad distribution of less than 1.07; and the storage modulus G′ of said polymer, determined upon cooling as described herein, intersecting a value of 3.10 5  Pa at a temperature of less than 85 ° C. The invention also describes polymerization processes suitable for the manufacture of these adhesive alpha-olefin inter-polymers.

RELATED APPLICATIONS:

[0001] The present application is based on Provisional Application Ser.No. 60/199,093, filed on Apr. 21, 2000, and on Provisional ApplicationSer. No. 60/171,715, filed on Dec. 21, 1999.

FIELD OF INVENTION

[0002] Adhesive alpha-olefin inter-polymers, adhesive compositions orformulations comprising such inter-polymers for adhesive application andadhesion processes and articles in which adhesive compositions orformulations are used.

BACKGROUND OF INVETION

[0003] Certain alpha-olefin inter-polymers have been used in adhesivecompositions which should yield a significant bond strength afterapplication, show good paper adhesion (e.g. fiber tear on Kraft paper),minimum peel strength of 500 g/cm, low color, low odor, and good thermalstability. For PSA applications, when the substrate is an OPP tape, therolling ball tack test should yield a maximum of 3 cm at ambienttemperature, a S.A.F.T. minimum value of 85° C., a shear (12.5 mm×25 mmarea under a 1 Kg weight) on cardboard at 40° C. of at least 30 hours.Most known alpha-olefin inter-polymers in such compositions have a highmelting point and/or a high crystallinity. These characteristics preventsuch materials, on their own, from being used as an adhesive because anadhesive must a low crystallinity for flexibility and a low plateaumodulus, as well as a low viscosity in many applications. (see J.Adhesion Sci. Technol. Vol 3, No 7 pp551-570 (1989) where an SBSblock-copolymer is used).

[0004] In such prior art adhesive formulations, the alpha-olefininter-polymers contribute to the bond-strength, but tackifiers are usedto increase the Tg for good bond strength and bring the high plateaumodulus down to an acceptable level by decreasing the polymer chainentanglements. Flow promoters (waxes etc) are used to improve the flowand ensure wetting of the substrate by the formulation. Withouttackifiers and flow promoters, such inter-polymers can be used to heatseal at reduced temperatures but are not, generally, regarded asadhesives.

[0005] The inter-polymers are derived predominantly from ethylene orpropylene (For ethylene based polymers see WO97-15636-A1; WO99/24516;WO9803603 (EP-912646) by way of example using single site catalyst;WO97-15636-A1 or WO94/10256; U.S. Pat. No. 5,317,070 and WO94/04625,using syndiotactic polypropylene as the polymer component, andmentioning on page 7 line 14 of hexene as comonomer. For propylene basedpolymers further see EP-318049. For basic monomers other than propyleneor ethylene, see for example EP-422498 a butene-propylene inter-polymerwith up to 20 wt % propylene derived units).

[0006] As an example of the inter-polymers used for heat sealing orimpact modification, reference is made to JP62-119212-A2. This disclosesa random copolymer with from 40-90 mole % of propylene, from 10-60 mole% of an alpha-olefin such as butene, hexene, and 4-methylpentene using ametallocene type ethylene-bis tetrahydro-indenyl zirconium dichloride asa catalyst. Similarly JP62-119213-A2 discloses a random copolymer ofbutene (60-98 mole %) with 2-40 mole % of C3-20 alpha-olefin such aspropylene, hexene, and 4-methylpentene.

[0007] However, the Examples in JP62-119212-A2 have widely varyingcharacteristics. Example 6 polymerizes propylene and hexene to give 60percent of units derived from propylene and 40 mol % of units derivedfrom hexene. The crystallinity is 26% and the melting point is 123° C.Example 3 uses propylene at 45 mol % with a melting point of 50° C. anda crystallinity 7%. JP62-119212-A2 does not disclose a polymer having acombination of structural characteristics (molecular weight; comonomercontent for example) such that a storage modulus G′ suitable foradhesive applications is reached below 70° C. or providing a low meltingpeak. The polymers are said to have anti-blocking characteristics andare of no use in adhesive applications.

[0008] WO99/67307 discloses a terpolymer comprising predominantlypropylene derived units for use as films, fibers, and molded articles,and also seal layers. The polymers in Table 4 have low comonomercontents, high melting points and high molecular weights.

[0009] WO9920644 discloses elastic composition of propylene homopolymersfor adhesive application. Metallocenes are used in the polymerization.

[0010] In other documents, alpha-olefin inter-polymers are preparedusing a conventional Ziegler-Natta catalyst with a titanium chloridetransition metal component and an aluminum alkyl activator to give apolymer with a monomer composition in which the amounts of propylene(lower molecular weight comonomer) and higher molecular weight comonomerare approximately equivalent have been suggested for adhesiveapplication. These have been referred to as A(morphous) P(oly) A(lpha)O(lefin), APAO's for short.

[0011] US-3954697 discloses in example 1 a propylene-hexene-l copolymercontaining 43 mol % of hexene-1 derived units which can be coated onto atape hot to give a pressure sensitive adhesive material. The polymer maybe used without additives (See column 2 lines 34 to 39) and can beapplied as a hot melt to a tape without solvent to show PSA behavior. InUS-3954697, the amount of hexene deemed essential for a polymer is inexcess of 40 mol % and the polymer structure must be such that that thepolymer is entirely amorphous and has no residual crystallinity (SeeColumn 3 lines 24 to 26) or crystallinity of a very low order (Seecolumn 4 line 8). For example, comparative Example 9 uses 18 mol %hexene in the polymer and obtains a melting point of 145° C. suggestingthe absence of Theological characteristics or melting points associatedwith satisfactory adhesive behavior. This polymer lacks tackiness atambient temperature.

[0012] High propylene content APAO with butene comonomer have been madeand sold under the Registered trade name Rextac using non-SSC typecatalysts. WO98/42780 discusses the use of such polymers in adhesivecompositions.

[0013] More details on such inter-polymers and their use in adhesivecompositions can be found in U.S. Pat. No. 5478891. U.S. Pat. No.5723546 uses blends to obtain the desired characteristics. Details canbe derived from U.S. Pat. No. 4217428, U.S. Pat. No. 4178272 and U.S.Pat. No.3954697 which recommend generally high amounts of the highermolecular weight alpha-olefin comonomer.

[0014] WO9823699 and EP 620257 disclose a polymer in which from 70 to 99mol % is derived from a C6 to C12 alpha-olefin and the remainder is alower alpha-olefin. The exemplified combinations are of hexene-propyleneand octene-ethylene inter-polymers prepared with a conventionalZiegler-Natta catalyst. A low Tg can be obtained. The material may becross-linked to improve cohesive strength. Nevertheless there aredrawbacks associated with such polymers and their application inadhesive end uses. Such known APAO's are non-homogenous, havesignificant levels of extractables and unsatisfactory physicalproperties, including low cohesive strength, that restrict theapplication and adhesive performance.

SUMMARY OF INVENTION

[0015] The invention relates (I) to novel adhesive alpha-olefininter-polymers which are largely amorphous and have a Theologicalbehavior that makes them suitable for adhesive use. In this aspect, theinvention also relates to processes for the manufacture of theseadhesive alpha-olefin inter-polymers.

[0016] In one aspect the invention provides a polymer which is suitablefor adhesive use and has a sufficiently high storage modulus uponcooling, without relying unduly on the presence of lower molecularweight components such as a tackifier (which can create problems ofexcessive migration of its constituents and requires blending) or lowmolecular impurities formed in the course of polymerization and/or whichhas a low melting point with a narrow melting range and/or which has amonomer distribution pattern which provides an improved balance of lowmelting point and cohesive strength. Therefore in one aspect theinvention provides an adhesive composition or formulation which containsno or low amounts of tackifier, yet provides a satisfactory balance ofproperties for an adhesive composition.

[0017] Advantages of the invention include improved polymers which canbe used with reduced amounts of, or possibly no tackifier, in order toprovide a hot melt adhesive composition or formulation. These polymerscan be used with reduced amounts of, or possibly no solvent, in order toprovide a adhesive formulations with reduced environmental impact.Further, another embodiment of the invention provides sprayable adhesiveformulations, including sprayable HMA compositions, comprisingpredominantly of polymers having a reduced plateau modulus and/ormolecular weight.

[0018] In one specific embodiment the invention provides in a firstaspect a poly-alpha olefin inter-polymer comprising

[0019] A) from 60 to 94% of units derived from one alpha mono-olefinhaving from 3 to 6 carbon atoms and

[0020] B) from 6 to 40 mol % of units derived from one or more othermono-olefins having from 4 to 10 carbon atoms and at least one carbonatom more than A); and

[0021] C) optionally from 0 to 10 mol % of units derived from anothercopolymerizable unsaturated hydrocarbon, different from A) and B);

[0022] the diad distribution of component A in the polymer as determinedby ¹³C NMR as described herein showing a ratio of experimentallydetermined diad distribution over the calculated Bemoullian diaddistribution of less than 1.07; and

[0023] the storage modulus G′ of said polymer, determined upon coolingas described herein, intersecting a value of 3.10⁵ Pa at a temperatureof less than 85° C.

[0024] In another aspect there is provided a poly-alpha olefininter-polymer having (I)

[0025] A) from 60 to 94% of units derived from one alpha mono-olefinhaving from 3 to 6 carbon atoms and B) from 6 to 40 mol % of unitsderived from one or more other mono-olefins having from 4 to 10 carbonatoms and at least one carbon atom more than A); and optionally from 0to 10 mol % of units derived from another copolymerizable unsaturatedhydrocarbon, different from A) and B);

[0026] the diad distribution of component A in the polymer as determinedby ¹³C NMR as described herein showing a ratio of experimentallydetermined diad distribution over the calculated Bemoullian diaddistribution of less than 1.07; and

[0027] said polymer having a melting behavior as determined by DSC, asdescribed herein, so that Tm (interpolymer) is less than 153−2.78×[CB+C] for any given concentration of B) and/or C) components whereT_(m) is the major melting peak of the interpolymer at a given contentof components B) and C) in mol %; [C_(B+C)] is the mol % of component B)plus C).

[0028] The invention thus further relates (II) to adhesive compositionswhich consist predominantly of the inter-polymer and to formulations foradhesive end-uses comprising the inter-polymer and in addition limitedamounts of other components such a) tackifiers for lowering the plateaumodulus and/or b) flow promoters such as low molecular weight additivesfor lowering the viscosity of the formulation in its molten state duringthe application of the formulations onto a substrate. Anti-oxidants,stabilisers etc. may also be present in the composition andformulations.

[0029] Such compositions or formulations may be a hot melt adhesive(HMA) and be applied to a substrate in the substantial absence ofsolvent or diluent at above ambient temperature to initiate adhesion andthen cool to ambient temperature to establish a bond.

[0030] Such compositions or formulations may be a pressure sensitiveadhesive (PSA) and be applied in the substantial absence of solvent ordiluent to a substrate to initiate adhesion at ambient temperature. Ifthe PSA is applied hot to its substrate to form an article, for examplea tape or label which is subsequently used at ambient temperature toinitiate adhesion, the PSA is known as a hot melt pressure sensitiveadhesive (HMPSA).

[0031] Such compositions or formulations may be applied as a solution inthe presence of a suitable solvent for the components, to give a solventbased adhesive (SBA). Such solutions are applied to substrate and thesolvent is evaporated. For example, the adhesive layer then actssimilarly to the HMPSA and is called a solvent-based pressure sensitiveadhesive (SBPSA).

[0032] The invention additionally relates (III) to processes using suchcompositions or formulations as well as articles obtained by suchprocesses. For example the compositions and formulations of theinvention can be sprayed, preferably in filamentary form, onto asubstrate for use in packaging and for disposable items, such asdiapers, and other sanitary articles or can be used for adhesive tape.

BRIEF DESCRIPTION OF THE DRAWINGS

[0033]FIG. 1 illustrates the DSC melting behavior as defined herein fora prior art Rextac RT 2715 grade and a inter-polymer according to theinvention of Example 1;

[0034]FIG. 2 illustrates the DSC melting peaks against the comonomercontent, for Rextac RT 2715, Examples of the invention herein, andExamples of JP62-119212-A2 referred to herein

[0035]FIG. 3 plots G′ versus the temperature during a progressivecooling cycle according to the method described herein for the polymerof Example 1 and Example 3;

[0036]FIG. 4 represent the obtained NMR graph of the polymer of Example1 and the peak assignment is used to calculate the polymermicrostructure for this and other examples.

DETAILED DESCRIPTION OF THE INVENTION

[0037] The selection of the monomer contents for the inventioninter-polymers can be combined with the selection of the physicalproperties to provide a polymer which provides an effective polymericbackbone in an adhesive and requires no or reduced amounts of additionalcomponents to achieve the desired balance of processing and adhesiveproperties. Preferably then A) is derived from units having from 3 to 6carbon atoms and is most preferably propylene; B) is derived from unitshaving from 4 to 10 carbon atoms, preferably at least one more carbonatoms than A), and is most preferably butene-1, hexene-1 or octene-1,and C) is derived from ethylene.

[0038] Preferably the polymer is a random copolymer having astatistically random distribution of component B) and substantially freeof blocks of adjacent one or other of the monomer component B) asdetermined by NMR. The randomness can be provided in continuousprocessing by a sufficient level of back-mixing in the reactor. In batchprocesses as used in the examples herein, a sufficient randomness can beprovided by ensuring that the finishing monomer composition does notvary excessively from the initial polymer composition. Suitably anybatch reaction should be stopped at a relatively low monomer conversion.

[0039] These monomers can be readily polymerized using metallocene basedcatalyst systems to provide low extractability and good adhesivebehavior.

[0040] Suitably the inter-polymer contains at least 65 mol % (for goodcrystallinity and bond-strength) and/or no more than 90 mol % of unitsderived from A) to avoid excessive crystallinity and undesirablestiffness. Advantageously the inter-polymer has a crystallinity of atleast 3% and/or no more than 20%, preferably at least 5 mol % and/or nomore than 15% as determined by DSC. Suitably the adhesive composition orformulation as applied as an adhesive has a heat of fusion of from 5 to33 J/g.

[0041] The structure and crystallinity of the inter-polymer of theinvention also influences the melting point. Preferably theinter-polymer has a major melting peak as determined by DSC of at least40° C. and/or no more than 130° C., preferably a melting peak of atleast 50° C. and/or no more than 90° C. Low levels of crystallinityshould provide the inter-polymer with necessary cohesive strengthwithout significant compromise of the adhesive performance while themelting behavior determines its application temperature.

[0042] By selecting an inter-polymer with a suitable Tg, one can alsoreduce or eliminate the need to blend the polymer with a tackifier.Advantageously the inter-polymer has a Tg of at least minus 40° C.and/or no more than minus 5° C., preferably at least minus 30° C. and/orno more than minus 10° C.

[0043] The polymer can also be selected by reference to the Theologicalbehavior and preferably has a G′ value of less than 0.3 MPa in atemperature window somewhere between the end-use temperature and theprocessing temperature. With such a low elastic modulus, the adhesiveexhibits high deformability during bond formation, and thus caneffectively wet the substrate to which it is applied. This is aprerequisite to achieve an adhesive bond of sufficient strength.

[0044] The inter-polymer of the invention may have any Mw/Mn value aslong as the extractability is low as indicated before. When ametallocene based catalyst system is used, the optimum way of achievingthe low extractability is to rely on the narrow Mw/Mn which isadvantageously from 1.5 to 4, especially from 1.8 to 3.5.

[0045] As a result of the contribution made by the polymer to theadhesive behavior of the adhesive composition or formulation, thecomposition or formulation may be used without relying on solvent, e.g.substantially free of volatile components, and contain no or less than25 wt % of tackifier, preferably less than 20 wt %. Alternatively theinvention includes formulating the adhesive in a suitable solvent (SBA).

[0046] Depending on the location of the tan δ as determined by rheologymeasurements, the composition may be applied as a HMA, PSA, or SBA.

[0047] For optimum use as HMA to be applied by spreading or coating,preferably the inter-polymer composition or formulation uses aninter-polymer having a Melt Index from 1 to 2000 as determined underASTM D1238 method, preferably at least 5, and especially a least 10 andpreferably no more than 1000, and especially no more than 500.

[0048] For optimum use as HMA to be applied by spraying, preferably theinter-polymer composition or formulation uses an inter-polymer having aMelt Index flowability of at least 1000.

[0049] While the inter-polymer contributes to the adhesive behavior,nevertheless it may be desirable to complement that by relying on otheringredients in the formulation. Optionally then the composition orformulation may further comprise from 1 to 25 wt % of a tackifier and/orfrom 1 to 20 wt % of flow improver.

[0050] For optimum use as PSA to be applied by coating, preferably theadhesive comprises an inter-polymer having a Melt Index from 1 to 5000as determined under ASTM D1238 method preferably 20 to 3000, andespecially 100 to 2000.

[0051] The adhesives containing the inter-polymer may be used in makinghygienic articles containing a structure, elements of which are adheredby a composition or formulation as described above.

[0052] Process of Polymerization

[0053] The catalyst selected should generally be suitable for preparingpolymers and copolymers from olefinically, vinylically andacetylenically unsaturated monomers.

[0054] In its broadest form the invention can be performed with any SSC(single sited) catalyst. These generally contain a transition metal ofGroups 3 to 10 of the Periodic Table; and at least one ancillary ligandthat remains bonded to the transition metal during polymerization.Preferably the transition metal is used in a reduced cationic state andstabilized by a cocatalyst or activator. Especially preferred aremetallocenes of Group 4 of the Periodic table such as titanium, hafniumor zirconium which are used in polymerization in the d⁰ mono-valentcationic state and have one or two ancillary ligands as described inmore detail hereafter. The important features of such catalysts forcoordination polymerization are the ligand capable of abstraction andthat ligand into which the ethylene (olefinic) group can be inserted.

[0055] The metallocene can be used with a cocatalyst, which may bealumoxane, preferably methylalumoxane, having an average degree ofoligomerization of from 4 to 30 as determined by vapor pressureosmometry. Alumoxane may be modified to provide solubility in linearalkanes but is generally used from a toluene solution. Such solutionsmay include unreacted trialkylaluminum and the alumoxane concentrationis generally indicated by mol Al per liter, which figure includes anytrialkyl aluminum which has not reacted to form an oligomer. Thealumoxane, when used as cocatalyst, is generally used in molar excess,at a mol ratio of from at least 50 preferably at least 100 and no morethan 1000, preferably no more than 500.

[0056] The metallocene may be also be used with a cocatalyst which is anon- or weakly coordinated anion (these term non-coordinating anion asused herein includes weakly coordinated anions). The coordination shouldbe sufficiently weak in any event, as evidenced by the progress ofpolymerization, to permit the insertion of the unsaturated monomercomponent.) The non-coordinating anion may be supplied and reacted withthe metallocene in any of the manners described in the art.

[0057] The precursor for the non-coordinating anion may be used with ametallocene supplied in a reduced valency state. The precursor mayundergo a redox reaction . The precursor may be an ion pair of which theprecursor cation is neutralized and/or eliminated in some manner. Theprecursor cation may be an ammonium salt as in EP-277003 and EP-277004.The precursor cation may be a triphenylcarbonium derivative.

[0058] The non-coordinating anion can be a halogenated,tetra-aryl-substituted Group 10-14 non-carbon, element-based anion,especially those that are have fluorine groups substituted for hydrogenatoms on the aryl groups, or on alkyl substituents on those aryl groups.

[0059] The effective Group 10-14 element cocatalyst complexes of theinvention are, in a preferable embodiment, derived from an ionic salt,comprising a 4-coordinate Group 10-14 element anionic complex, whereA⁻can be represented as:

[(M)Q ₁ Q ₂ . . . Q ₁]⁻,

[0060] where M is one or more Group 10-14 metalloid or metal, preferablyboron or aluminum, and either each Q is ligand effective for providingelectronic or steric effects rendering [(M′)Q₁Q₂ . . . Q_(n)]− suitableas a non-coordinating anion as that is understood in the art, or asufficient number of Q are such that [(M′)Q₁Q₂ . . . Q_(n)]⁻ as a wholeis an effective non-coordinating or weakly coordinating anion. ExemplaryQ substituents specifically include fluorinated aryl groups, preferablyperfluorinated aryl groups, and include substituted Q groups havingsubstituents additional to the fluorine substitution, such asfluorinated hydrocarbyl groups. Preferred fluorinated aryl groupsinclude phenyl, biphenyl, napthyl and derivatives thereof.

[0061] Representative metallocene compounds can have the formula:

L ^(A) L ^(B) L ^(C) _(i MDE)

[0062] where, L^(A) is a substituted cyclopentadienyl orheterocyclopentadienyl ancillary ligand π-bonded to M; L^(B) is a memberof the class of ancillary ligands defined for L_(A), or is J, aheteroatom ancillary ligand σ-bonded to M; the L^(A) and L^(B) ligandsmay be covalently bridged together through a Group 14 element linkinggroup; L^(c) _(i) is an optional neutral, non-oxidizing ligand having adative bond to M (i equals 0 to 3); M is a Group 4 or 5 transitionmetal; and, D and E are independently monoanionic labile ligands, eachhaving a π-bond to M, optionally bridged to each other or L^(A) orL^(B). The mono-anionic ligands are displaceable by a suitable activatorto permit insertion of a polymerizable monomer or macromonomer caninsert for coordination polymerization on the vacant coordination siteof the transition metal component.

[0063] Non-limiting representative metallocene compounds includemono-cyclopentadienyl compounds such aspentamethylcyclopentadienyltitanium isopropoxide,pentamethylcyclopentadienyltribenzyl titanium,dimethylsilyltetramethyl-cyclopentadienyl-tert-butylamido titaniumdichloride, pentamethylcyclopentadienyl titanium trimethyl,dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconiumdimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdimethyl, unbridged biscyclopentadienyl compounds such as bis(1,3-butyl,methylcyclopentadienyl.) zirconium dimethyl,pentamethylcyclopentadienyl-cyclopentadienyl zirconium dimethyl,(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdimethyl; bridged bis-cyclopentadienyl compounds such asdimethylsilylbis(tetrahydroindenyl) zirconium dichloride andsilacyclobutyl(tetramethylcyclopentadienyl)(n-propyl-cyclopentadienyl)zirconium dimethyl; bridged bisindenyl compounds such asdimethylsilylbisindenyl zirconium dichloride, dimethylsilylbisindenylhafnium dimethyl, dimethylsilylbis(2-methylbenzindenyl) zirconiumdichloride, dimethylsilylbis(2-methylbenzindenyl) zirconium dimethyl;and fluorenyl ligand-containing compounds, e.g.,diphenylmethyl(fluorenyl)(cyclopentadienyl)zirconium dimethyl; and theadditional mono- and biscyclopentadienyl compounds such as those listedand described in U.S. Pat. Nos. 5,017,714, 5,324,800 and EP-A-0 591 756.All documents are incorporated by reference for purposes of U.S. patentpractice.

[0064] Preferred metallocenes include bridged chiral biscyclopentadienyl derivatives which comprise a fused ring system of anindenyl. Suitably these are substituted in the 2-position relative tothe bridge. Most preferred are such compounds with no furthersubstitution other than that in the 2 position.

[0065] Representative non-metallocene transition metal compounds usableas SSC's also include tetrabenzyl zirconium, tetrabis(trimethylsiylmethyl) zirconium, oxotris(trimethlsilylmethyl)vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, bis(hexamethyldisilazido)dimethyl titanium, tris(trimethyl silyl methyl) niobiumdichloride, tris(trimethylsilylmethyl) tantalum dichloride.

[0066] Additional organometallic transition metal compounds suitable asolefin polymerization catalysts in accordance with the invention will beany of those Group 3-10 that can be converted by ligand abstraction intoa catalytically active cation and stabilized in that active electronicstate by a noncoordinating or weakly coordinating anion sufficientlylabile to be displaced by an olefinically unsaturated monomer such asethylene.

[0067] Exemplary SSC compounds include those described in the patentliterature. U.S. Pat. No. 5,318,935 describes bridged and unbridgedbisamido transition metal catalyst compounds of Group 4 metals capableof insertion polymerization of α-olefins. International patentpublications WO 96/23010, WO 97/48735 and Gibson, et. al., Chem. Comm.,pp. 849-850 (1998), disclose diimine-based ligands for Group 8-10 metalcompounds shown to be suitable for ionic activation and olefinpolymerization. See also WO 97/48735. Transition metal polymerizationcatalyst systems from Group 5-10 metals wherein the active transitionmetal center is in a high oxidation state and stabilized by lowcoordination number polyanionic ancillary ligand systems are describedin U.S. Pat. No. 5,502,124 and its divisional US patent 5,504,049. Seealso the Group 5 organometallic catalyst compounds of U.S. Pat. No.5,851,945 and the tridentate ligand containing Group 5-10 organometalliccatalyst compounds of copending U.S. application Ser. No. 09/302243,filed Apr. 29, 1999, and its equivalent PCT/US99/09306. Bridgedbis(arylamido) Group 4 compounds for olefin polymerization are describedby D. H. McConville, et al, in Organometallics 1995, 14, 5478-5480.Synthesis methods and compound characterization are presented. Furtherwork appearing in D. H. McConville, et al, Macromolecules 1996, 29,5241-5243, described bridged bis(arylamido) Group 4 compounds that areactive catalysts for polymerization of 1-hexene. Additional transitionmetal compounds suitable in accordance with the invention include thosedescribed in WO 96/40805. Cationic Group 3 or Lanthanide metal complexesfor coordination polymerization of olefins is disclosed in copendingU.S. application Ser. No. 09/408050, filed Sept. 29, 1999, and itsequivalent PCT/US99/22690. The precursor metal compounds are stabilizedby a monoanionic bidentate ancillary ligand and two monoanionic ligandsand are capable of activation with the ionic cocatalysts of theinvention. Each of these documents is incorporated by reference for thepurposes of U.S. patent practice.

[0068] When using the catalysts of the invention, the total catalystsystem will generally additionally comprise one or more organometalliccompound as scavenger. Such compounds as used in this application aremeant to include those compounds effective for removing polar impuritiesfrom the reaction environment and for increasing catalyst activity.Impurities can be inadvertently introduced with any of thepolymerization reaction components, particularly with solvent, monomerand catalyst feed, and adversely affect catalyst activity and stability.It can result in decreasing or even elimination of catalytic activity,particularly when ionizing anion pre-cursors activate the catalystsystem. The polar impurities, or catalyst poisons include water, oxygen,metal impurities, etc. Preferably steps are taken before provision ofsuch into the reaction vessel, for example by chemical treatment orcareful separation techniques after or during the synthesis orpreparation of the various components, but some minor amounts oforganometallic compound will still normally be used in thepolymerization process itself.

[0069] Typically these compounds will be organometallic compounds suchas the Group-13 organometallic compounds of U.S. Pat. Nos. 5,153,157,5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and that ofWO 95/07941. Exemplary compounds include triethyl aluminum, triethylborane, triisobutyl aluminum, methylalumoxane, and isobutylaluminumoxane. Those compounds having bulky or C₆-C₂₀ linear hydrocarbylsubstituents covalently bound to the metal or metalloid center beingpreferred to minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as triisobutylaluminum, triisoprenylaluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexylaluminum,tri-n-octylaluminum, or tri-n-dodecylaluminum. When alumoxane is used asactivator, any excess over the amount needed to activate the catalystspresent can act as a poison scavenger compound and additionalorganometallic compounds may not be necessary. Alumoxanes also may beused in scavenging amounts with other means of activation, e.g.,methylalumoxane and triisobutyl-aluminoxane with boron-based activators.The amount of such compounds to be used with catalyst compounds of theinventions is minimized during polymerization reactions to that amounteffective to enhance activity (and with that amount necessary foractivation of the catalyst compounds if used in a dual role) sinceexcess amounts may act as catalyst poisons.

[0070] The catalysts may be used advantageously in homogeneous solutionprocesses. Random polymerization in homogeneous conditions furtherpromotes the homogeneity of the resulting polymer. Generally thisinvolves polymerization in a continuous reactor in which the polymerformed and the starting monomer and catalyst materials supplied, areagitated to reduce or avoid concentration gradients. Suitable processesinclude are performed above the melting point of the polymers at highpressure at from 10 to 3000 bar in which the monomer acts as diluent orin solution polymerization using an alkane solvent.

[0071] Each of these processes may also be employed in singular,parallel or series reactors. The liquid processes comprise contactingolefin monomers with the above described catalyst system in a suitablediluent or solvent and allowing said monomers to react for a sufficienttime to produce the invention copolymers. Hydrocarbyl solvents aresuitable, both aliphatic and aromatic, hexane is preferred. Generallyspeaking, the polymerization reaction temperature can vary from 40° C.to 250° C. Preferably the polymerization reaction temperature will befrom 60° C. to 220°. The pressure can vary from about 1 mm Hg to 2500bar, preferably from 0.1 bar to 1600 bar, most preferably from 1.0 to500 bar.

[0072] The process can be carried out in a continuous stirred tankreactor, or more than one operated in series or parallel. These reactorsmay have or may not have internal cooling and the monomer feed my or maynot be refrigerated. See the general disclosure of U.S. Pat. No.5,001,205 for general process conditions. See also, internationalapplication WO 96/33227 and WO 97/22639. All documents are incorporatedby reference for US purposes for description of polymerizationprocesses, metallocene selection and useful scavenging compounds.

EXAMPLES

[0073] The following Examples are for illustrative purposes only. TheTests and measurements used in the claims and the following examples areperformed as follows:

[0074] Measuring Method I

[0075] Dynamic Theological properties were determined with a RMS800equipment manufactured by Rheometric Scientific, Piscataway, New Jersey.In order to better simulate the real-life process where the materials isapplied in the molten state and subsequently cooled down, dynamic moduliwere recorded when decreasing temperature from 120 C. down to -20 C. Theoutput of the test is therefore the evolution of the storage modulus G′,the loss modulus G″, as well as the ratio tanδ=G″/G′ as a function oftemperature. Measurements were made at a constant frequency of 1 Hz,using a 12.5 mm diameter plate-and-plate geometry. In order to performmeasurements at sub-ambient temperatures, liquid nitrogen cooling devicewas used throughout the whole test, which was minimizing at the sametime the risk of thermal-oxidative degradation at high temperature. Inorder to compensate for dimension changes during the experiments(thermal expansion of tools and samples, as well as sample shrinkageduring crystallization) the gap between the two plates wereautomatically adjusted so to keep a slight constant compression force onthe sample. Due to the broad range of mechanical behavior investigated(from the molten state down to the glassy region), the magnitude of thedeformation applied was also adjusted during the test in order to keepthe force level between measurable limits, and remain well within thelinear viscoelastic region at all times.

[0076] DSC-peak melting point and crystallinity were determined using aprocedure that described as follows. A predetermined amount of samplepressed at approximately 150° C. to 200° C. to form a film. A centralpiece of the film (preferably 7 to 12 mg) is removed with a punch dieand annealed for 120 hours at room temperature. Thereafter, DSC data wasobtained (TA Instruments 2920 temperature modulated DSC) by cooling thesample at −50° C. and subsequently heating it at 10 C/min to 150° C.where it stays isothermally for 5 min before a second cooling-heatingcycle is applied. Both the first and second cycle thermal events arerecorded. The maximum melting peak is recorded as Tm and the area underthe endothermic transition is used to calculate the crystallinitypercent. The crystallinity percent is calculated using the formula,[area under the curve (Joules/gram)/165 (Joules/gram)] * 100.

[0077] The NMR methodology was the following. The sample was prepared bydissolving +/−0.5 g of polymer in 2.5 ml of TCB (trichlorobenzene), towhich later 0.5 ml of Deuterobenzene was added. The analysis wasperformed at 300 MHz NMR instrument, at 125 degree C, the acquisitiontime was 2 sec, delay 38 sec, full decoupling, 1024 transients. Thereactivity ratio was determined using the formula 4*PP*HH/(PH+HP)2.Bemouillian behavior implies that there is no influence from the lastcomonomer unit in the growing chain on the next one coming in, thereforeincorporation is only depended on monomer concentration in the feed. Aperfectly Bemouillian system would have a product of reactivity ratiosof r_(a)*r_(b)=1. For example, Rextac (a Ziegler-Natta propylenecopolymer) has a product reactivity ratios of 1.3, polymer in presentinvention between 0.9<r_(a)*r_(b)<1.1. Therefore these polymers are muchmore Bernullian than the Rextac. Polymer Sequence Determination, J. C.Randall, Academic Press 1977.

[0078] All molecular weights are weight average molecular weight unlessotherwise noted. Molecular weights (weight average molecular weight (Mw)and number average molecular weight (Mn) were measured by Gel PermeationChromatography, unless otherwise noted, using a Waters 150 GelPermeation Chromatograph equipped with a differential refractive indexdetector and calibrated using polystyrene standards. Samples were run ineither THF (45° C.) or in 1,2,4-trichlorobenzene (145° C.) dependingupon the sample's solubility using three Shodex GPC AT-80 MIS columns inseries. This general technique is discussed in “Liquid Chromatography ofPolymers and Related Materials III^(i)” J. Cazes Ed., Marcel Decker,1981, page 207, which is incorporated by reference for purposes of U.S.patent practice herein. No corrections for column spreading wereemployed; however, data on generally accepted standards, e.g. NationalBureau of Standards Polyethylene 1475, demonstrated a precision with 0.1units for Mw/Mn which was calculated from elution times. The numericalanalyses were performed using Expert Ease software available from WatersCorporation.

[0079] Examples of inter-polymers

[0080] The following examples are presented. All parts, proportions andpercentages are by weight unless otherwise indicated. All examples werecarried out in dry, oxygen-free environments and solvents. Although theexamples may be directed to certain embodiments of the presentinvention, they are not to be viewed as limiting the invention in anyspecific respect. The polymers are prepared on a laboratory scale usingbatch reactors with stirring. In these examples certain abbreviationsare used to facilitate the description. These include standard chemicalabbreviations for the elements. Melt Index (MI) values in thedescription and claims were measured according to ASTM D 1238 conditionE at 190° C. with a 2.16 kg. load.

[0081] The toluene was further dried over a sodium/potassium alloy.Triethylaluminum was purchased from Akzo Nobel. Elemental Analyses wereperformed by Galbraith Laboratories, Inc.

[0082] Preparation of Polymer

Example 1

[0083] 300 ml of prepurified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slight positive argon atmosphere atall times. Consequently, 2 ml solution of 10% wt. methylaluminoxane intoluene, supplied by Aldrich, was transferred into the autoclave. 40 mlof prepurified hexene was added and the mixture was stirred until stablepressure was reached. The reactor was maintained at a pressure slightlyabove atmospheric. In succession, 50 g of prepurified propylene wasadded under stirring. The reactor mixture was heated to 90° C. At thisreactor temperature premixed 2 mg ofdimethylsilyl-bis(2-methyl4-phenylindenyl)zirconium dichloride (1 mg/lmlof toluene) and 2 ml solution of 10 wt. % methylaluminoxane in toluenewere placed in the reactor. The polymerization was conducted for 30minutes. The product which was soluble in hexane was precipitated twicein acidified isopropanol. Thereafter, the product was filtered and driedunder reduced pressure for 24 hr. The yield was 48 g.

[0084] The composition as determined by NMR was 73% mole propylene and27% mole hexene derived units. The molecular weights and molecularweight distribution from GPC were: Mn=46 k, Mw=93 k, Mz=168 k,Mw/Mn=2.04.

[0085] The DSC showed Tm=41° C. this melting point was observed only atthe first heating (See FIG. 1). This due to the fact that the materialcrystallizes slowly (depending on the material crystallization can takedays or even weeks). The crystallinity during the first heating was6.7%. The glass transition was minus 23° C.

Example 2

[0086] The polymerization was conducted in the same way as in Example 1except that the supplied monomer proportions were changed. 73 g ofproduct were obtained. From NMR data the composition was 74 mole %propylene and 26 mole % hexene. The DSC data showed Tm=43° C.,crystallinity 7% and Tg=−21° C. The molecular weight information wereobtained from GPC (Mw=99 k, Mn=44 k, Mz=160 k, Mw/Mn=2.24).

Example 3

[0087]500 ml of purified and degassed toluene was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive N₂ atmosphere at alltimes. Consequently, lml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. Then, 40 ml of prepurifiedhexene was added and the mixture was stirred until a stable pressure wasreached. The reactor was maintained at a positive pressure (i.e.slightly above atmospheric). In succession, 150 ml of prepurified liquidpropylene was added under stirring. The reactor mixture was heated to95° C. At this reactor temperature premixed 0.5 mg ofdimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride (1mg/Iml of toluene) and Iml solution of 10 wt. % methylaluminoxane intoluene were placed in the reactor. The polymerization was conducted for20 minutes. The product which was soluble in hexane was precipitated inslightly acidified isopropanol. Thereafter, the product was filtered,washed and dried under reduced pressure for 24 hr. The yield was 75.8 g.

[0088] The composition was determined by NMR (91.9% mole propylene and8.1% mole hexene). The molecular weights and molecular weightdistribution from GPC data were: Mn=11 k, Mw-25 k, Mw/Mn=2.2.

[0089] The DSC showed Tm=95° C. (melting peak), Tc=50° C. Thecrystallinity was 18%. The glass transition temperature was minus 6° C.

Example 4

[0090] The polymerization procedure described in Example 1 wassubstancially followed conducted in the same way as in except that thesupplied monomer proportions were slightly changed, anddimethylsilyl-bis(2-methyl-indenyl)zirconium dichloride (1 mg/1 ml oftoluene) was the used catalyst. The product which was soluble in hexanewas precipitated in isopropanol. Thereafter, the product was filteredand dried under reduced pressure for 24 hr. The yield was 70 g.

[0091] The composition was determined by NMR (79% mole propylene and 21%mole hexene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=14 k, Mw=28 k, Mz=44 k, Mw/Mn=2.0.

[0092] The DSC showed Tm=45° C. this melting point was observed only atthe first heating. The crystallinity during the first heating was 10%.The glass transition was −22° C.

Example 5

[0093] The polymerization was conducted in the same way as in Example 4except that 60 ml of hexene was introduced into the autoclave and thereaction temperature was 75° C. Also scavenger, catalyst and cocatalystsupply were cut to half. 54 g of product were obtained. From NMR datathe composition was 74 mole % propylene and 26 mole % hexene. The DSCdata showed Tm=42° C., crystallinity 11% and Tg=-23° C. The molecularweight information were obtained from GPC (Mw=108 k, Mn=56 k, Mz=171 k,Mw/Mn=1.93).

Example 6

[0094]500 ml of purified and degassed toluene was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive N₂ atmosphere at alltimes. Consequently, lml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. Then, 60 ml of prepurifiedhexene was added and the mixture was stirred until a stable pressure wasreached. The reactor was maintained at a positive pressure (i.e.slightly above atmospheric). In succession, 100 ml of prepurified liquidpropylene was added under stirring. The reactor mixture was heated to60° C. At this reactor temperature premixed 0.5 mg ofdimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride (1mg/lml of toluene) and lml solution of 10 wt. % methylaluminoxane intoluene were placed in the reactor. The polymerization was conducted for20 minutes. The product which was soluble in hexane was precipitated inslightly acidified isopropanol. Thereafter, the product was filtered,washed and dried under reduced pressure for 24 hr. The yield was 68 g.

[0095] The composition was determined by NMR (91% mole propylene and 9%mole hexene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=55 k, Mw=105 k, Mw/Mn=l.9.

[0096] The DSC showed Tm=86° C. (melting peak), Tc=25° C. Thecrystallinity was 15%. The glass transition temperature was minus 8° C.Example 7

[0097] 400 ml of purified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slight positive argon atmosphere atall times. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 15 ml of purified hexene wasadded and the mixture was stirred until stable pressure. The reactor wasmaintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 80° C. At this reactor temperature premixed and sufficientlyaged, 0.8 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloride(mg/ml of toluene) and 1 ml solution of 10 wt. % methylaluminoxane intoluene were placed in the reactor. The polymerization was conducted for10 minutes. Threafter, the reactor was cooled down and vented to theatmosphere. The product, which was soluble in hexane, was precipitatedin slightly acidified isopropanol. Thereafter, the product was washed,filtered and dried under reduced pressure for 24 hr. The yield was 20 g.

[0098] The composition was determined by NM (93.6% mole propylene/6.4%mole hexene).

[0099] The DSC showed melting peak at 94° C., crystallization peak at48° C. The crystallinity was 18%. The glass transition was -12° C.

Example 8

[0100] 300 ml of purified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive argon atmosphere atall times. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 15 ml of purified octene wasadded and the mixture was stirred until stable pressure. The reactor wasmaintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 90° C. At this reactor temperature premixed and sufficientlyaged, 0.8 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloridedissolved in 1 ml toluene (1 mg/1 ml) and 1 ml solution of 10 wt. %methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 15 minutes. Threafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 46 g.

[0101] The composition was determined by NMR 93.2% mole propylene/6.8%mole octene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=223 k, Mw=50 k, Mz=91 k, Mw/Mn=2.16.

[0102] The DSC showed melting peak at 94° C. The crystallinity was 20%.Example 9

[0103] 300 ml of purified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive argon atmosphere atall times. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 45 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 85° C. At this reactor temperature premixed and sufficientlyaged, 1 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloridedissolved in 1 ml toluene (1 mg/1 ml) and 1 ml solution of 10 wt. %methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 30 minutes. Thereafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 51.5 g.

[0104] The composition was determined by NMR 90.7% mole propylene 9.3%mole 1-butene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=24 k, Mw=59 k, Mz=136 k, Mw/Mn=2.5.

[0105] The DSC showed melting peak at 110° C. and crystallization peakat 70° C. and Tg at −8 OC.

Example 10

[0106] 400 ml of purified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive argon atmosphere atall times. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 30 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 85° C. At this reactor temperature premixed and sufficientlyaged, 0.2 ml dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride dissolved in 1 ml toluene (1 mg/1 ml) and 0.5 ml solution of10 wt. % methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 15 minutes. Threafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 21.5 g.

[0107] The composition was determined by NMR 81.4% mole propylene/18.6%mole 1-butene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=88 k, Mw=190 k, Mz=318 k, Mw/Mn=2.16.

[0108] The DSC showed melting peak at 105° C. crystallization peak at63° C. The crystallinity was 24% and the Tg was -9° C.

Example 11

[0109] 400 ml of purified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive argon atmosphere atall times. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 40 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 85° C. At this reactor temperature premixed and sufficientlyaged, 0.2 ml dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride dissolved in 1 ml toluene (1 mg/1 ml) and 0.5 ml solution of10 wt. % methylaluminoxane in toluene were placed in the reactor. Thepolymerization was conducted for 15 minutes. Thereafter, the reactor wascooled down and vented to the atmosphere. The product, which was solublein hexane, was precipitated in slightly acidified isopropanol.Thereafter, the product was washed, filtered and dried under reducedpressure for 24 hr. The yield was 40 g.

[0110] The composition was determined by NMR 71.4% mole propylene/23.1%mole octene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=88 k, Mw=182 k, Mz=298 k, Mw/Mn=2.06.

[0111] The DSC showed melting peak at 96° C. crystallization peak at 52°C. The crystallinity was 22% and the Tg was -16° C.

Example 12

[0112] 400 ml of purified and degassed hexane was transferred into astainless steel autoclave reactor with internal capacity of 1000 ml. Thereactor had been maintained under slightly positive argon atmosphere atall times. Consequently, 1.5 ml solution of 10% wt. methylaluminoxane intoluene was transferred into the autoclave. 60 ml of purified 1-butenewas added and the mixture was stirred until stable pressure. The reactorwas maintained at a slightly positive pressure. In succession, 50 g ofprepurified propylene was added under stirring. The reactor mixture washeated to 95° C. At this reactor temperature premixed and sufficientlyaged, 1 ml dimethylsilyl-bis(2-methyl-indenyl)zirconium dichloridedissolved in 1 ml toluene (lmg/lml) and 1 ml solution of 10 wt. %methylaluminoxane in toluene and 2 ml of purified hexane were placed inthe reactor. The polymerization was conducted for 15 minutes.Thereafter, the reactor was cooled down and vented to the atmosphere.The product, which was soluble in hexane, was precipitated in slightlyacidified isopropanol. Thereafter, the product was washed, filtered anddried under reduced pressure for 24 hr. The yield was 56.6 g.

[0113] The composition was determined by NMR 67.3% mole propylene/26.7%mole 1-butene). The molecular weights and molecular weight distributionfrom GPC data were: Mn=19 k, Mw=40 k, Mz=70 k, Mw/Mn=2.22.

[0114] The DSC showed melting peak at 63° C. crystallization peak at 23°C. The crystallinity was 13%andtheTgwas-21° C.

[0115] Table 1 summarizes the polymerisation conditions and polymercharacteristics of the preceding Examples.

[0116] The Table 2 shows the 13C NMR results for the preceding Examples.

[0117] Table 3 provides data on the adhesive performance of selectedpolymers made as described above in IA application.

[0118] Given that the polymers of the invention can be utilized withoutthe use of tackifiers it is likely that they can be applied by spraying.Continuous fiberization techniques involve the fast stretching of a hotmelt filament extruded through a nozzle. Therefore, good flow-ability inthe nozzle itself is required and the ability to maintain a continuousfilament without break is needed. The polymers of the invention have anarrow molecular weight distribution, similar to the polymers alreadyused in sprayable formulations such as triblock styrenic copolymers ormetallocene catalyzed plastomers (EP-858489, WO-9715636). The elasticityin the molten state is reduced, therefore, the occurrence of undesirablehigh stresses in the stretched filament are avoided. In contrary tohighly tackified systems, the substantial absence of low molecularweight species (i.e. tackifiers, plasticizers) in the current inventionprovides a further guarantee of the cohesion of the systems in themolten state, since nearly all molecules are long enough to entanglewith each other. This will further delay the undesired cohesion break ofthe hot melt filament during spraying operations, thereby opening newavenues for even faster line speeds.

[0119] The polymers of the invention were also applied from a solventsolution with a minor amount of tackifier. An easy release performancewas shown, which due to the absence of non-polymeric contaminantsindicates suitability in applications where no residue may be left onthe surface after tape removal, such as medical tape.

[0120] The polymers of the invention are also intended for use inadhesives, sealing, and coatings. They may be added as hot melts aloneor with other components such as tackifiers, antioxidants, crystallinitymodifiers, etc. They may added in a suitable solvent alone or with othercomponents such as tackifiers, antioxidants, crystallinity modifiers,etc. and the solvent is evaporated after application on a substrate.TABLE 1 Co- Al/Zr Mol % Mw Tm Tg Crystallinity Example TM catalyst molratio C3⁼ Comonomer x[10³] Mw/Mn [° C.] [° C.] X % 1dimethylsilyl-bis(2-methyl-4- MAO 1000 73 Hexene 93 2.0 41 −23 6.7phenylindenyl)zirconium dichloride 2 dimethylsilyl-bis(2-methyl-4- MAO1000 75 Hexene 99 2.2 43 −21 7.0 phenylindenyl)zirconium dichloride 3dimethylsilyl-bis(2-methyl-4- MAO 2000 92 Hexene 25 2.2 95 −6 18phenylindenyl)zirconium dichloride 4 dimethylsilyl-bis(2-methyl- MAO 80079 Hexene 28 2.0 45 −22 10 indenyl)zirconium dichloride 5dimethylsilyl-bis(2-methyl- MAO 800 74 Hexene 108 1.9 42 −23 11indenyl)zirconium dichloride 6 dimethylsilyl-bis(2-methyl-4- MAO 2000 90Hexene 105 1.9 86 −8 15 phenylindenyl)zirconium dichloride 7dimethylsilyl-bis(2-methyl- MAO 1000 94 Hexene 96 2.3 94 −12 18indenyl)zirconium dichloride 8 dimethylsilyl-bis(2-methyl- MAO 1000 93Octene 50 2.2 94 −17 20 indenyl)zirconium dichloride 9dimethylsilyl-bis(2-methyl- MAO 800 90.7 Butene 59 2.5 110 −8 25indenyl)zirconium dichloride 10 dimethylsilyl-bis(2-methyl-4- MAO 500081.4 Butene 190 2.2 105 −9 23 phenylindenyl)zirconium dichloride 11dimethylsilyl-bis(2-methyl-4- MAO 5000 71.4 Butene 180 2.1 96 −16 21phenylindenyl)zirconium dichloride 12 dimethylsilyl-bis(2-methyl- MAO800 67.3 Butene 40 2.2 63 −21 13 indenyl)zirconium dichloride

[0121] TABLE 2 Mole fraction Mole fraction of PP PP diad Reactivity ofPP diads diads (Bernullian, (exp.)/PP ratios example (experimental)calculated) diad (calc.) R_(A) × R_(B) Rextac 0.488 0.454 1.075 1.35 10.537 0.543 0.989 0.92 2 0.540 0.543 0.995 0.93 3 0.846  .847 0.999 0.854 0.632 0.627 1.008 1.18 5 0.551 0.546 1.009 1.14 6 0.828 0.829 0.9990.85 7 0.877 0.876 1.001 1.13 8 0.870 0.869 1.001 1.12 9 0.823 0.8231.000 1.06 10  0.659 0.662 0.995 0.87 11  0.586  0.5912 1.009 0.85 12 0.538 0.537 1.002 1.04

[0122] TABLE 3 HMA Evaluation- Polymer applied neat Rextac RT 2715 at.150° C. Neat Polymer 5 1 2 Viscosity at 180° C. 2280  14800  1920  3030 (mPas) (Brookfield As 8. /Spindle 21) Softening Point (° C.)   109.5  72.5  75   72.5 (Average of 2 Samples) 109.3/109.06 72.3/75.674.7/75.9 73.7/72.4 (Herzog As 1.) Coating. (° C.) (Acumeter 150 150 150150 As 1.) Press Lamination at . . . 110 (PE)/150 (AL 110 (PE)/150 (AL110 (PE)/150 (AL 110 (PE)/150 (AL (° C.) (PHI Press. 4400 & PP) & PP) &PP) & PP) Psi for 30 s.) T - Peel at Roomtemp. on 478 455 480 375 PE.G/cm) (Average of 3 Samples.) Adhesion Failure. Adhesion Failure.Adhesion Failure. Adhesion Failure. 410/400/380 450/375/540 T - Peel atRoomtemp. on 397 432 387 302 Al. G/cm) (Average of 3 Samples.) AdhesionFailure. Adhesion Failure. Adhesion Failure. Adhesion Failure.410/400/380 430/450/415 T - Peel at Roomtemp. on 498 542 400 370 PP.G/cm) (Average of 3 Samples.) Adhesion Failure. Adhesion Failure.Adhesion Failure. Adhesion Failure. 410/400/380 450/375/540 Hot Shear.(Min)  25  5  26  28 (1″ × ½″ × 1 Kg./ 25/28/21 5/6/5 31/29/19 23/29/33Average of 3 Samples.) S.A.F.T.(° C.)  52  42   48.5  42 (1″ × ½″ × 0.5Kg./ 51.3/52.9/51.8 42.2/42.8/41.7 49.2/46.5/49.7 41.7/42.8/42.2 Averageof 3 Samples.) Static Shear at 60° C.    4.5  1  3  1 (Min.) (1″ × ½″ ×1 Kg./ 4/5/4 1/1/1 4/3/2 1/1/1 Average of 3 Samples.)

1. A poly-alpha olefin inter-polymer comprising A) from 60 to 94% ofunits derived from one alpha mono-olefin having from 3 to 6 carbon atomsand B) from 6 to 40 mol % of units derived from one or more othermono-olefins having from 4 to 10 carbon atoms and at least one carbonatom more than A); and C) optionally from 0 to 10 mol % of units derivedfrom another copolymerizable unsaturated hydrocarbon, different from a)and b); the diad distribution of component a in the polymer asdetermined by ¹³C NMR as described herein showing a ratio ofexperimentally determined diad distribution over the calculatedbemoullian diad distribution of less than 1.07; and the storage modulusG′ of said polymer, determined upon cooling as described herein,intersecting a value of 3.10⁵ pa at a temperature of less than 85° c: 2.An inter-polymer according to claim 1 in which the content of B)combined with C) is at least 8 mol % and/or less than 40 mot % and thestorage modulus G′ of said polymer determined upon cooling as describedherein, intersecting a storage modulus G′ of 3.105 Pa at a temperatureof less than 70° C.
 3. An inter-polymer according to claim 1 in whichthe reactivity ratio as determined by NMR as described herein, has avalue of R_(A)×R_(B), wherein R_(A) is the reactivity ratio of componentA over component B and R_(B) is the ratio of component B over componentA, of less than 1.4.
 4. An inter-polymer according to claim 1 where theweight average molecular weight of the polymer as determined by GPC asdescribed herein, is less than 120 000, preferably less than 90 000, andmost preferably less than 70 000 and/or at least 20 000, preferably atleast 30 000 and especially at least 40 000, the storage modulus G′ ofsaid polymer, determined upon cooling as described herein, intersectinga storage modulus G′ of 3.10⁵ Pascal at a temperature of less than 70°C.5. An inter-polymer according to claim 1 which A) is derived from unitshaving from 3 to 6 carbon atoms and preferably propylene; B) is derivedfrom units having from 4 to 8 carbon atoms, preferably at least two morecarbon atoms than A), and is preferably butene-1, hexene-1 or octene-1,and C) is derived from ethylene.
 6. An inter-polymer according to claim1 in which said polymer having a melting behavior as determined by DSC,as described herein, wherein the major peak melting point varies withcontent of component B) plus C) so that T_(m) (interpolymer) is lessthan 153−2.78×[C_(B+C)] for any given concentration of B) and/or C)components. Where Tm is the major melting peak of the interpolymer at agiven content of components B) and C) in mol %; [C_(B+C)] is the mol %of component B) plus C).
 7. An inter-polymer according to claim 1 inwhich there are at least 65 mol %, preferably at least 75 mol % of unitsderived from A) and/or no more than 94 mol %, preferably no more than 90mol % of A); at least 6 mol %, preferably at least 10 mol % of B) and/orno more than 30 mol %, preferably no more than 25 mol % of B); and/or nomore than 5 mol %, most preferably no more than 2 mol % of C).
 8. Aninter-polymer according to claim 1 which has a heat of fusion of atleast 5 J/g, preferably at least 10 J/g and/or no more than 40 J/g,preferably no more than 30 J/g, and most preferably no more than 20 J/gas determined by DSC as described herein.
 9. An inter-polymer accordingto claim 1 which has a major melting peak as determined by DSC, asdescribed herein, of at least 40° C., preferably of at least 50° C.and/or has a melting point as determined by DSC of no more than 130° C.,preferably no more than 90° C.
 10. An inter-polymer according to claim 1which has a Tg determined by DSC, as described herein, of no more thanminus 5° C., preferably no more than minus −15° C., and/or at leastminus 40° C., preferably at least minus 30° C.
 11. An inter-polymeraccording to claim 1 which G′ at 120° C. is not greater than 1000Pascal, preferably not greater than 500 Pascal and most preferably nogreater than 100 Pascal.
 12. An inter-polymer according to claim 1having an Mw/Mn as determined by GPC, as described herein, of from 1.5to 4, more preferably less than 3, most preferably less than 2.2 and/orat least 1.6.
 13. A poly-alpha olefin inter-polymer having A) from 60 to94% of units derived from one alpha mono-olefin having from 3 to 6carbon atoms and B) from 6 to 40 mol % of units derived from one or moreother mono-olefins having from 4 to 10 carbon atoms and at least onecarbon atom more than A); and C) optionally from 0 to 10 mol % of unitsderived from another copolymerizable unsaturated hydrocarbon, differentfrom A) and B); the diad distribution of component A in the polymer asdetermined by ¹³C NMR as described herein showing a ratio ofexperimentally determined diad distribution over the calculatedBemoullian diad distribution of less than 1.07; and said polymer havinga melting behavior as determined by DSC, as described herein, so thatT_(m) (interpolymer) is less than 153−2.78×[C_(B+C)] for any givenconcentration of B) and/or C) components where T_(m) is the majormelting peak of the interpolymer at a given content of components B) andC) in mol %; [C_(B+C)] is the mol % of component B) plus C).
 14. Aninterpolymer according to claim 13 in which the storage modulus G′ ofsaid polymer, determined upon cooling as described herein, intersectinga value of 3.10⁵ Pascal at a temperature of less than 85° C.
 15. Aninter-polymer according to claim 13 which the content of B) combinedwith C) is at least 8 mol % and/or less than 40 mol % and the storagemodulus G′ of said polymer, determined upon cooling as described herein,intersecting a storage modulus G′ of 3.10⁵ Pascal at a temperature ofless than 70° C.
 16. An interpolymer according to claim 13 in which thereactivity ratio as determined by NMR as described herein, has a valueof R_(A)×R_(B), wherein R_(A) is the reactivity ratio of component Aover component B and R_(B) is the ratio of component B over component A,of less than 1.4.
 17. An interpolymer according to claim 13 in which theweight average molecular weight of the polymer as determined by GPC asdescribed herein, is less than 120 000, preferably less than 90 000, andmost preferably less than 70 000 and/or at least 20 000, preferably atleast 30 000 and especially at least 40 000, the storage modulus G′ ofsaid polymer, determined upon cooling as described herein, intersectinga storage modulus G′ of 3.10⁵ Pascal at a temperature of less than 70°C.18. An interpolymer according to claim 13 in which A) is derived fromunits having from 3 to 6 carbon atoms and preferably propylene; B) isderived from units having from 4 to 8 carbon atoms, preferably at leasttwo more carbon atoms than A), and is preferably butene-1, hexene-1 oroctene-1 and C) is derived from ethylene.
 19. An interpolymer accordingto claim 13 in which there are at least 65 mol %, preferably at least 75mol of units derived from A) and/or no more than 94 mol %, preferably nomore than 90 mol % of A); at least 6 mol %, preferably at least 10 mol %of B) and/or no more than 30 mol %, preferably no more than 25 mol % ofB); and/or no more than 5 mol %, most preferably no more than 2 mol % ofC).
 20. An interpolymer according to claim 13 which has a heat of fusionof at least 5 J/g, preferably at least 10 J/g and/or no more than 40J/g, preferably no more than 30 J/g, and most preferably no more than 20J/g as determined by DSC as described herein.
 21. An interpolymeraccording to claim 13 which has a melting peak as determined by DSC ofat least 40° C., preferably of at least 50° C. and/or has a meltingpoint as determined by DSC of no more than 130° C., preferably no morethan 95° C.
 22. An interpolymer according to claim 13 which has a Tgdetermined by DSC of no more than minus 5° C., preferably no more thanminus 20° C., and/or at least minus 40° C., preferably at least minus30° C.
 23. An interpolymer according to claim 13 which the G′ at 120° C.is not greater than 1000 Pascal, preferably not greater than 500 Pascal;and most preferably no greater than 100 Pascal.
 24. An interpolymeraccording to claim 13 having an Mw/Mn as determined by GPC as describedherein of from 1.5 to 4, more preferably less than 3, most preferablyless than 2.2 and/or at least 1.6.
 25. An adhesive composition orformulation containing an inter-polymer according to claim 13 which issubstantially free of volatile components, containing less than 20 wt %,preferably less than 10 wt % of tackifier and optionally less than 3 wt% each of anti-oxidant, flow improver, wax, or crystallization aid. 26.An adhesive composition or formulation according to claim 25 furthercomprising from 1 to 20 wt % of a tackifier and/or from 1 to 20 wt % ofa flow improver.
 27. An adhesive composition or formulation according toclaim 25 for use as a hot melt adhesive in which the Melt Index is from1 to 2000 as determined under ASTM D1238 methods.
 28. An adhesivecomposition or formulation according to claim 25 having a flowability ofat least and being suitable for applying the adhesive composition byspraying.
 29. An adhesive composition or formulation according to claim25 for use as a pressure sensitive adhesive in which the Melt Index isfrom 0.1 to 200 as determined under ASTM D1238 method.
 30. An adhesivecomposition or formulation according to claim 25 which contains at least10 wt %, preferably at least 20 wt % of the total weight of theformulation and no more than 90 wt % of a hydrocarbon based volatilesolvent, preferably no more than 60 wt % of the total weight of theformulation.
 31. A packaging material or article containing a structure,elements of which are adhered by an adhesive composition or formulationaccording to claim
 25. 32. A hygienic garment containing a structure,elements of which are adhered by an adhesive composition or formulationaccording to claim
 25. 33. An process for adhering two substratestogether which process comprises (I) applying a poly-alpha olefininter-polymer having A) from 55 to 94% of units derived from one alphamono-olefin having from 3 to 6 carbon atoms and B) from 6 to 45 mol % of% of units derived from one or more other mono-olefins having from 4 to10 carbon atoms and at least one carbon atom more than A); and C)optionally from 0 to 10 mol % of units derived from anothercopolymerizable unsaturated hydrocarbon, different from A) and B) thediad distribution of component A in the polymer as determined by ¹³C NMRas described herein showing a ratio of experimentally determined diaddistribution over the calculated Bernoullian diad distribution of lessthan 1.07 (II) to the interface between the substrate at elevatedtemperature of from 10 to 100° C. and/or pressure until adhesion isestablished.